JP2006124526A - Amide-based wax and fluidity controlling agent containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide amide-based wax capable of being used as a component of a fluidity controlling agent to be added to a nonaqueous coating and having excellent fluidity controlling properties and dispersibility in water, and to provide the fluidity controlling agent containing the wax and excellent in wettability to water. <P>SOLUTION: This amide-based wax for controlling fluidity contains a fatty acid diamide of 4-22C fatty acids with primary diamines and a polyoxyethylene chain-containing nonionic surfactant. The fluidity controlling agent contains the amide-based wax. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an amide wax and a water dispersible flow regulator containing the same and added to a non-aqueous paint or the like.

  The non-aqueous paint is added with a flow regulator so that it can be applied smoothly and cleanly.

  The flow modifier improves fluidity when stirring, makes it easier to apply paint on the object to be coated, reduces fluidity immediately after application, and makes the coating formed from the paint difficult to drip and smooth. It is. For example, Patent Document 1 discloses a fatty acid polyamide-based wax composed of an aliphatic primary diamine having 2 to 6 carbon atoms, hydroxystearic acid, and an aliphatic dicarboxylic acid having 2 to 10 carbon atoms.

  Non-aqueous paints added with flow control agents such as fatty acid polyamide-based waxes, for example non-aqueous paints added with flow control agents to resin components such as acrylic resins that are cured by active energy rays such as ultraviolet rays and electron beams, A resist image that forms a desired pattern on the object to be coated when it is applied to the object to be coated, and a part of the formed film is cured to form a water-insoluble cured material, and the uncured film on the unexposed part is washed and removed. Is formed.

  Such fatty acid amide waxes are excellent in flow controllability, but are generally hydrophobic and have low compatibility with water. Therefore, when this uncured coating is washed with water, it is likely to aggregate and precipitate. There is a problem that the precipitated wax remains on the surface of the coating film.

JP-A-5-271585

  The present invention has been made in order to solve the above problems, and is an amide wax having excellent flow controllability and water dispersibility, which is a component of a flow control agent added to a non-aqueous paint, and contains it Another object of the present invention is to provide a flow regulator excellent in water wettability.

  The invention according to claim 1 made to achieve the above object includes a fatty acid diamide of a fatty acid having 4 to 22 carbon atoms and a primary diamine, and a polyoxyethylene chain-containing nonionic surfactant. It is an amide type wax characterized by having.

  This fatty acid diamide is, for example, a wax-like compound synthesized by amidation reaction of fatty acids and primary diamines. The polyoxyethylene chain-containing nonionic surfactant may be mixed during the synthesis of the fatty acid diamide, or may be mixed in a molten state after the synthesis of the fatty acid diamide.

  Since this amide wax is derived from the ether group in the polyoxyethylene chain-containing nonionic surfactant and has high hydrophilicity, it exhibits excellent water dispersibility.

  Similarly, the invention according to claim 2 is a flow regulator comprising the amide wax according to claim 1.

  The flow modifier preferably contains at least 10% by weight of an amide wax.

  Similarly, the invention according to claim 3 is characterized in that the polyoxyethylene chain-containing nonionic surfactant and the fatty acid diamide are contained in a weight ratio of 4: 6 to 1: 9. It is the described flow regulator.

  When the weight ratio of the polyoxyethylene chain-containing nonionic surfactant is more than 4: 6, flow controllability such as thixotropy that improves fluidity during stirring and lowers fluidity during standing. On the other hand, when it is less than 1: 9, water dispersibility is not expressed.

  Similarly, the invention according to claim 4 is characterized in that the polyoxyethylene chain-containing nonionic surfactant has a hydrophile-lipophile balance (HLB) of at least 13. It is a flow regulator.

  The hydrophilic oily balance is a scale indicating the hydrophilicity of a nonionic surfactant, and for example, Griffin's HLB is famous. The calculation formula is represented by HLB = (molecular weight of hydrophilic group portion / molecular weight of surfactant) × 20 of the nonionic surfactant. If the hydrophilic oil balance is less than 13, the hydrophilicity is too low to improve the water dispersibility of the flow modifier.

  Similarly, the invention according to claim 5 is the flow regulator according to claim 2, wherein the polyoxyethylene chain-containing nonionic surfactant is solid or pasty at room temperature.

  If the polyoxyethylene chain-containing nonionic surfactant is liquid at room temperature of 25 ° C., the amide wax mixed with fatty acid diamide is too soft and cannot be used as a flow regulator.

  Similarly, the invention according to claim 6 is the flow regulator according to claim 2, wherein the fatty acid contains 12-hydroxystearic acid.

  The fatty acid may be 12-hydroxystearic acid alone, and contains at least 60% by weight of 12-hydroxystearic acid as a main component and another fatty acid having 4 to 22 carbon atoms as a subcomponent. It may be a mixture.

  Similarly, the invention according to claim 7 is characterized in that the amide wax is finely divided into particles having an average particle size of 30 μm at the maximum and heat-treated in an organic solvent. It is an agent.

  When the average particle size of the amide wax exceeds 30 μm, thixotropic properties are hardly exhibited. It is more preferable that the average particle diameter of the amide wax is finely divided to 10 μm or less.

  This flow regulator is added to a paint such as a non-aqueous paint.

  When the paint is left standing, the amide wax fine particles are gradually attracted by a relatively weak interaction such as hydrogen bonding. As a result, the coating material is gelled and exhibits a thickening property, and thus it is difficult for the coating material to flow while dispersing pigments and the like. When the paint is agitated, the weak and reversible interaction is broken up by the kinetic energy in a very short time. As a result, the viscosity of the paint is drastically reduced, and the paint becomes sol and easily flows. Therefore, the coating material exhibits appropriate fluidity that is easy to apply with a brush or the like. As soon as the coating film is formed by applying the paint, kinetic energy from the outside, such as during stirring or application, is no longer supplied, so the weak interaction is restored in a very short time. As a result, the coating material forming the film is less likely to flow again and less likely to sag. In this way, the paint is excellent in thixotropic properties by the flow regulator.

  This paint is derived from the ether group of the polyoxyethylene chain-containing nonionic surfactant in the amide wax and has high hydrophilicity to water. For this reason, the amide wax exhibits appropriate wettability when a part of the film is cured, and is well dispersed in water when the remaining part of the uncured film is washed with water.

  The amide wax of the present invention is useful as a component of a flow regulator to be added to a non-aqueous paint, and exhibits excellent flow adjustability and water dispersibility. The flow regulator containing it is easy to disperse in water. A non-aqueous paint containing a flow modifier exhibits excellent thixotropy that it is easy to apply and the film formed by application is difficult to drip. When the coating is cured, it becomes a cured product having appropriate wettability. On the other hand, when the coating is not cured, the flow modifier is dispersed in water without agglomeration and is removed by washing with water.

  Hereinafter, examples of the amide wax of the present invention and a flow regulator containing the amide wax will be described in detail.

  The amide wax of the present invention is obtained by mixing and dispersing a polyoxyethylene chain-containing nonionic surfactant in a fatty acid diamide prepared by an amidation reaction of a fatty acid having 4 to 22 carbon atoms and a primary diamine. It is.

The polyoxyethylene chain-containing nonionic surfactant may be premixed and mechanically dispersed together with the fatty acid having 4 to 22 carbon atoms and the primary diamine during the preparation of the fatty acid diamide. After being allowed to mix, they may be mixed and dispersed.

As a polyoxyethylene chain-containing nonionic surfactant, for example,
Neugen ET-190, Neugen YX-400, Neugen YX-500, Neugen ET-189, Neugen ONo. 190, (both are trade names manufactured by Daiichi Kogyo Seiyaku Co., Ltd.);
In addition, NIKKOL HCO-50, NIKKOL HCO-60, NIKKOL HCO-80, NIKKOL HCO-100 (both trade names manufactured by Nikko Chemical Co., Ltd.), Braunon RCW-60, Braunon, which are polyoxyethylene addition-cured castor oils RCW-80, BROWNON RCW-100, BROWNON CW-200 (all trade names manufactured by Aoki Oil & Fat Co., Ltd.);
Polyoxyethylene-added fatty acid esters, Brownon S-1000A, Brownon O-700SA, Brownon DS-6000 (both trade names manufactured by Aoki Oil & Fat Co., Ltd.), Ramigen ES-100 (Daiichi Kogyo Seiyaku Co., Ltd.) Product name);
Examples include Epan 680 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is polyoxyethylene polyoxypropylene glycol.

  Examples of fatty acids having 4 to 22 carbon atoms constituting the fatty acid diamide include 12-hydroxystearic acid; butyric acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid used therewith.

  Examples of primary diamines constituting the fatty acid diamide include 1,6-hexamethylenediamine, 1,4-diaminobutane, ethylenediamine, metaxylenediamine, and Jeffamine EDR-148 (trade names manufactured by Sun Techno Chemical Co., Ltd.). It is done.

  Amide wax, for example, an amide wax comprising fatty acid diamide obtained by reacting 600 parts by weight of 12-hydroxystearic acid and 1/2 equivalent of 1,6 hexamethylenediamine, and 180 parts by weight of BROWNON DS6000 Is generally a light yellow to light tan solid.

  The acid value and amine value of the amide wax are preferably 15 or less, and more preferably 5 or less.

  The flow regulator of the present invention is obtained by pulverizing the amide wax with a dry pulverizer such as a jet mill until it has fine particles having an average particle size of 30 μm or less, preferably fine particles having an average particle size of 10 μm or less. After mixing and dispersing, the resulting dispersion mixture is prepared by heat treatment at 30 to 90 ° C, preferably 50 to 80 ° C for 1 to 50 hours.

  The flow regulator is a media-type wet disperser using glass beads or the like after the amide wax is crushed to an average particle size of 30 μm or less, preferably 10 μm or less, and then mixed with an organic solvent. Further, the mixture may be further pulverized to obtain a finely dispersed dispersion of fine particles having an average particle size of 30 μm or less, preferably 10 μm or less, and then heat-treated.

  Examples of the organic solvent include aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, esters, and alcohols.

  The flow control agent may contain additives such as a dispersant and a wetting agent.

  When this flow regulator, a resin component such as an acrylic resin that is cured by an active energy ray such as an ultraviolet ray or an electron beam, and a pigment as necessary are mixed, a non-aqueous paint is obtained. This paint is used as, for example, an ultraviolet curable resin, a non-aqueous paint, or a coating agent.

  Examples in which amide waxes and flow control agents to which the present invention is applied are prepared are shown in Examples 1 to 8, and examples in which amide waxes and flow control agents other than the present invention are applied are shown in Comparative Examples 1-2. Shown in

Example 1
To a 1 L four-necked flask equipped with a stirrer, a thermometer, and a water separator, 600.0 parts by weight of 12-hydroxystearic acid, which is a fatty acid, is added, and further, brownon, which is a polyoxyethylene chain-containing nonionic surfactant 120.0 parts by weight of S-1000A (trade name, manufactured by Aoki Oil & Fat Co., Ltd.) was added and heated to 110 to 120 ° C. to dissolve them. After cooling the flask to an internal temperature of 100 ° C., 116.0 parts by weight of hexamethylene diamine as a primary diamine was gradually added, heated to 130 to 140 ° C. and stirred for 30 minutes. Further, the temperature was slowly raised to 170 ° C. and dehydrated to carry out an amidation reaction. After reacting for 5 to 6 hours, a light yellow, massive amide wax (acid number 4.3; amine number 4.5) was obtained. This was passed through a pulverizer to obtain amide wax fine particles having an average particle size of 10.0 μm or less. 30 parts by weight of the amide wax fine particles and 270 parts by weight of propylene glycol monomethyl ether, which is an organic solvent, are placed in a 900 mL glass bottle, and 150 parts by weight of glass beads (φ = 1.5 mm) are added, and a paint shaker is used. Distributed processing was performed. The obtained dispersion mixture was filled in a sealed container and heat-treated at 60 to 65 ° C. for 12 hours to prepare a desired flow regulator.

(Example 2)
An amidation reaction was carried out using 131.2 parts by weight of metaxylenediamine in place of hexamethylenediamine of Example 1 to obtain a light yellow amide wax (acid value 4.0; amine value 4.3). The target flow regulator was prepared in the same manner as Example 1 except for the above.

(Example 3)
An amidation reaction was carried out using 88.0 parts by weight of 1,4 diaminobutane instead of hexamethylenediamine of Example 1 to obtain a light yellow amide wax (acid number 4.3; amine number 4.5). Except that, the target flow regulator was prepared in the same manner as in Example 1.

Example 4
An amidation reaction was carried out using 120.0 parts by weight of Neugen ET-207A (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) instead of Blaunon S-1000A of Example 1, and a pale yellow amide wax ( The target flow regulator was prepared in the same manner as in Example 1 except that the acid value was 4.6; the amine value was 3.0).

(Example 5)
An amidation reaction was carried out using 120.0 parts by weight of Lamigen ES-100 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) instead of Blaunon S-1000A of Example 1, and a pale yellow amide wax ( The target flow regulator was prepared in the same manner as in Example 1 except that the acid value 4.1; the amine value 4.6) was obtained.

(Example 6)
An amidation reaction was carried out using 120.0 parts by weight of Epan 680 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) instead of Blaunon S-1000A of Example 1, and a pale yellow amide wax (acid value) 4.2; the target flow regulator was prepared in the same manner as in Example 1 except that the amine value 4.0) was obtained.

(Example 7)
An amidation reaction was carried out using 120.0 parts by weight of Brownon CW-200 (trade name, manufactured by Aoki Oil & Fat Co., Ltd.) instead of Brownon S-1000A of Example 1, and a pale yellow amide wax (acid The target flow regulator was prepared in the same manner as in Example 1 except that the value 4.9; the amine value 3.8) was obtained.

(Example 8)
An amidation reaction was performed using 12-hydroxystearic acid and 1,6-hexamethylenediamine without using Epan 680 of Example 6, and after the reaction, Epan 680 was mixed with molten fatty acid diamide to obtain a pale yellow amide system. A flow regulator was prepared in the same manner as in Example 1 except that a wax (acid number 4.8; amine number 4.0) was obtained.

(Comparative Example 1)
An amidation reaction was carried out using 12-hydroxystearic acid and 1,6-hexamethylenediamine without using Blaunon S-1000A of Example 1, and a pale yellow amide wax (acid value 4.7; amine value 4). 0.1) was obtained in the same manner as in Example 1 except that a flow modifier was prepared.

(Comparative Example 2)
An amidation reaction was carried out using 12-hydroxystearic acid and metaxylenediamine without using Blaunon S-1000A of Example 2 to obtain a pale yellow amide wax (acid number 4.7; amine number 4.1). A flow regulator was prepared in the same manner as in Example 1 except that it was obtained.

  About the flow control agent obtained in Examples 1-8 and Comparative Examples 1-2, the water dispersibility evaluation test and the flow controllability evaluation test were done.

(Water dispersibility evaluation test)
70.0 g of ion-exchanged water and 1.0 g of each of the flow regulators of Examples 1 to 8 and Comparative Examples 1 and 2 were weighed into 140 ml glass bottles and dispersed with a paint shaker for 10 minutes to conduct a water dispersibility evaluation test. A sample was used. The obtained dispersion was allowed to stand, and the dispersibility was visually evaluated. A uniform dispersion with no aggregation observed ◎, a uniform dispersion with very little aggregation observed ◯, a slight aggregation observed ◯-△, a marked aggregation observed △, The agglomerated and sedimented materials were evaluated in 5 stages. The results are shown in Table 1.

(Flow adjustability evaluation test)
ACRIDIC A-801 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) 110.0 g, and 2.2 g of each of the flow regulators of Examples 1 to 8 and Comparative Examples 1 and 2, each 140 ml glass bottle The sample was weighed and mixed at 2500 rpm for 3 minutes using a disper to prepare a non-aqueous paint, which was used as a sample for physical property test. In addition, the thing of only ACRIDIC A-801 was used as the blank sample. Each sample was measured for viscosity (mPa · s) at 6 rpm and 60 rpm with a B-type viscometer. The viscosity at 6 rpm was divided by the viscosity at 60 rpm to calculate a TI value (Thixotropic Index). The higher the TI value, the better the thixotropic property. The results are shown in Table 1.

  As is apparent from Table 1, all of the flow regulators containing amide waxes composed of polyoxyethylene chain-containing nonionic surfactants and fatty acid diamides as in the examples have excellent water dispersibility. The non-aqueous paint had a high TI value, excellent fluidity at the time of coating, and excellent thixotropic properties such that the fluidity after coating was small, and the workability was good. On the other hand, the flow regulator containing an amide wax not containing a polyoxyethylene chain-containing nonionic surfactant as in the comparative example was not dispersed in water. In addition, the non-aqueous paint to which a flow control agent using an amide wax containing no polyoxyethylene chain-containing nonionic surfactant was added had a relatively low TI value and poor workability.

  The amide wax of the present invention is used as a component of a flow control agent that improves the workability of coating. The flow control agent containing this amide wax has excellent water dispersibility, so it is used by adding it to paints that apply plastic materials and building materials, and non-aqueous paints such as photoresist that remove unnecessary parts by washing with water. It is done.

Claims (7)

  An amide-based wax comprising a fatty acid diamide of a fatty acid having 4 to 22 carbon atoms and a primary diamine, and a polyoxyethylene chain-containing nonionic surfactant.   A flow regulator comprising the amide wax according to claim 1.   The flow regulator according to claim 2, wherein the polyoxyethylene chain-containing nonionic surfactant and the fatty acid diamide are contained in a weight ratio of 4: 6 to 1: 9.   The flow regulator according to claim 2, wherein the polyoxyethylene chain-containing nonionic surfactant has a hydrophilic oil balance of at least 13.   The flow regulator according to claim 2, wherein the polyoxyethylene chain-containing nonionic surfactant is solid or pasty at room temperature.   The flow regulator according to claim 2, wherein the fatty acid contains 12-hydroxystearic acid.   The flow control agent according to claim 2, wherein the amide wax is finely divided into particles having an average particle size of 30 µm at the maximum and heat-treated in an organic solvent.